EP2493962A1 - Procédé de production d'(hydroxyméthyl)polysiloxanes - Google Patents

Procédé de production d'(hydroxyméthyl)polysiloxanes

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Publication number
EP2493962A1
EP2493962A1 EP10763727A EP10763727A EP2493962A1 EP 2493962 A1 EP2493962 A1 EP 2493962A1 EP 10763727 A EP10763727 A EP 10763727A EP 10763727 A EP10763727 A EP 10763727A EP 2493962 A1 EP2493962 A1 EP 2493962A1
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EP
European Patent Office
Prior art keywords
formula
compounds
radical
equal
sir
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EP10763727A
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German (de)
English (en)
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EP2493962B1 (fr
Inventor
Jürgen Oliver DAISS
Jens Cremer
Elke Fritz-Langhals
Steffen Jungermann
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Wacker Chemie AG
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Wacker Chemie AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

  • the present invention relates to a method for
  • Methyl radical, and R 11 is a hydrocarbon radical
  • Siloxane skeleton is bound. If the OH group is reacted with other compounds, the resulting products are likewise bound to the siloxane skeleton in a manner stable to hydrolysis.
  • the group R 11 is a structuring factor which has both the properties of the (hydroxyalkyl) polysiloxane and the
  • (Hydroxyalkyl) polysiloxane resin as well as the properties of secondary products which can be prepared using the (hydroxyalkyl) polysiloxane or the (hydroxyalkyl) polysiloxane resin, co-determined.
  • the mobility of R 11 and the organic character of R 11 influence these properties.
  • the smallest possible radicals R 11 are ideal, particularly advantageous is the choice of R 11 equal to CH 2 .
  • Another benefit of this choice for R 11 is that small Structural units lower reaction volumes with the same amount of substance to R i: L- bonded OH groups and thus increased
  • DE 1 236 505 describes, inter alia, a process in which linear poly (dimethylsiloxane) (, co-OH-terminated) is reacted with an (acyloxymethyl) dimethylethoxysilane, and the si- (acyloxymethyl) groups are converted with methanol to form si- (hydroxymethyl
  • drastic conditions toluenesulfonic acid and heating
  • transesterification Si-CH 2 -OH transesterification
  • reaction "f) transesterification
  • DE 1 233 395 describes the preparation of (hydroxymethyl) -polysiloxanes or of (hydroxymethyl) polysiloxane resins by reacting (acyloxymethyl) polysiloxanes or (acyloxymethyl) polysiloxane resins with alkali metal borohydrides and hydrolysis of the primary product thus obtained
  • the object of the invention is therefore to improve the state of the art, to provide a process for the preparation of (hydroxymethyl) polysiloxanes or of (hydroxymethyl) polysiloxane resins, which leads to defined products, preferably in high purity and preferably with high product stability.
  • the invention relates to a process for preparing (hydroxymethyl) polysiloxanes or siloxane resins of poly ⁇ (hydroxymethyl) of the general formula I
  • Formula III are reacted, wherein a hydrogen atom or optionally with Q 1
  • a heteroatom-containing trivalent radical represents hydrogen, a group X-SiR 2 2 -, or together with Y represents a bonding electron pair,
  • Oxygen atom means
  • Meanings may be selected from the meanings of R 2 or Q 1 or Q 2 or represents a siloxane radical or a hydrolyzable group including hydroxyl or together with Z represents a bonding electron pair and may be connected to Z via X and by one or more optionally substituted siloxane
  • hydrolyzable group, or together with X represents an oxygen atom or is bonded to X or together with Z represents a bond
  • k, m, p, q are values greater than or equal to zero, with the proviso that the sum k + m + p + q means a sum of at least 2,
  • a takes the value 0 or 1.
  • Y is an oxygen atom
  • the compounds of formula II and of formula III or mixtures containing these compounds can be prepared in the inventive method in any order, mixed and metered to each other, optionally also multiply repeated, optionally also alternately.
  • at least one compound of the formula II and at least one compound of the formula III is used; it is also possible to use two, three, four, five, six or more compounds of the formula II or of the formula III, simultaneously or in succession, if appropriate also in multiply repeated form, optionally also alternately.
  • at least one (hydroxymethyl) polysiloxane or (hydroxymethyl) polysiloxane resin of the formula I is prepared; it is also possible to prepare two, three, four, five, six or more compounds of the formula I next to one another become.
  • the compounds of the formula III used can be free of solvolysates or, for example, theirs
  • Solvolysate for example with alcohols, water or
  • Formula III for the functionalization of Si-OH groups in organosiloxanes or organosiloxane resins of the general formula II, they react surprisingly easily and selectively with good yields with silanol groups to carbinols.
  • the inventive method differs from the previously known processes for the preparation of (hydroxymethyl) - polysiloxanes and (hydroxymethyl) polysiloxane resins.
  • siloxanes which have a grouping of the structure siloxane-CH 2 -A are used or produced as precursors.
  • organopolysiloxanes or organopolysiloxane resins of the formula II used in the process according to the invention are standard products of the silicone industry and thus need not be prepared separately as a precursor for the synthesis of (hydroxymethyl) polysiloxanes or (hydroxymethyl) polysiloxane resins.
  • R 1 and R 2 preferably have 1 to 12 carbon atoms, especially 1 to 6 carbon atoms, preferably only
  • R 1 and R 2 are straight-chain or branched or cyclic C 1 -C 6 hydrocarbon radicals.
  • the radicals are preferably methyl, ethyl, phenyl, allyl and vinyl, particularly preferably methyl.
  • the radicals are preferably methyl, ethyl, phenyl, allyl, vinyl, methoxy and ethoxy, particularly preferably methyl, ethyl, phenyl, allyl and vinyl,
  • the compounds of general formula I are preferably prepared in which R 1 and R 2 are methyl radicals.
  • Q 1 is preferably a fluorine, chlorine, bromine, iodine,
  • siloxanoxyalkyl siloxanoxyalkyl, siloxyaryl, siloxanoxyaryl, hydroxy, alkoxy, aryloxy, acyloxy, S-sulfonato, 0-sulfonato, sulfato, S-sulfinato, O-sulfinato, amino,
  • siloxanoxyalkyl siloxyaryl, siloxanoxyaryl, hydroxy, alkoxy, aryloxy, acyloxy, S-sulfonato, sulfato, amino, alkylamino, arylamino, dialkylamino, diarylamino, arylalkylamino, Acylamino, imido, sulfonamido, imino, mercapto, alkylthio or arylthio substituents, O-alkyl-IV-carbamato, O-aryl-N-carbamato, N-alkyl-O-carbamato, N-aryl-O- Carbamato, optionally alkyl- or aryl-substituted P-phosphonato, optionally alkyl or aryl-substituted 0-phosphonato, optionally alkyl or aryl-substituted P- optionally alkyl-
  • Q 2 preferably represents a heteroatom-containing divalent radical, for example -O-, -S-, -N (R 4 ) -, -C (O) -, epoxy, - C (O) -O-, -O-C (0) -O-, -O-C (O) -N (R 4 ) -, -N (R 4 ) -C (O) -O-, -S (O) -, -S (O) 2 -, -S (O) -O-, -S (O) 2 -O-, -O-S (O) 2 -O-, -O-S (O) 2 -O-, -C (O) -N (R 4 ) -, -S (O ) 2 -N (R) -, -S (O) 2 -N [C (O) R 6 ] -, -O-S (O) 2 -N (R 4 )
  • the hydroxy-functional organosiloxane of the general formula II can be, for example, linear, cyclic or branched.
  • the sum of k, m, p, q, s and t is preferably a number from 3 to 10,000, preferably 4 to 1000, more preferably 5 to 200.
  • the sum of k, m, p, q and r is preferably a number from 3 to 10,000, preferably 4 to 1000, more preferably 5 to 200.
  • the sum of k, m, p and q is preferably a number of 2 to 10,000, preferably from 3 to 1000, particularly preferably from 4 to 200
  • the named sums relate to the average
  • the groups [O1 / 2H] or the groups [Oi / 2 - (SiR 2 2 -XY-) a SiR 2 2 -CH 2 -OH] are bonded to groups (R ⁇ SiC ⁇ ).
  • k is preferably a number from 0 to 50, preferably 0 to 5, particularly preferably 0 to 1, in particular 0.
  • m is preferably a number from 0 to 100, preferably 0 to 10, particularly preferably 0 to 1, in particular 0.
  • p is preferably a number from 0 to 10,000, preferably 1 to 1000, particularly preferably 2 to 200.
  • q is preferably a number from 0 to 100, preferably 0 to 10, particularly preferably 0 to 1, in particular 0.
  • s is preferably a number from 1 to 100, preferably 1 bi
  • r is preferably a number from 1 to 100, preferably from 1 bi
  • t is preferably a number from 0 to 99, preferably from 0 to
  • the variable a preferably assumes the value 0 in formula I.
  • the groups [Oi / 2 H] are on the groups (R 1 2 Si0 2/2) is bound.
  • variable n preferably assumes values of greater than or equal to 2 in formula III, preferably values of 2 to 100, more preferably of 2 to 20.
  • the variable n can be, for example, 1, 2, 3, 4, 5 or 6-20 or assume bigger.
  • Y is preferably in formula III together with Z is a bond or Z is a group X-SiR 2 2 -, in the X together Z represents an oxygen atom or a siloxane group connected to Z; particularly preferably Y means
  • cyclic compounds of the formula III are obtained which consist exclusively of units [0-CH 2 -SiR 2 2] n .
  • a preferred variant for an organosiloxane of the general formula II is a linear silicone polymer with k and m equal to 0, p is greater than or equal to 1, q is 0 or 1 and r is 1 or
  • P is preferably from 3 to 10,000, preferably from 4 to 1000, particularly preferably from 5 to 200.
  • the stated values for p refer to the average chain lengths (number average) of the siloxanes.
  • r is s. The can
  • preferred organosiloxanes of general formula II be either monomodal or bimodal or multimodal,
  • branched organosiloxane of the general formula II is an organosilicone resin. This can consist of several units
  • Mol% of the units contained are denoted by the indices k, m, p, q, r, s and t. Preference is given to a value of 0.1 to 20 mol% of units r, based on the sum of k, m r Pr ⁇ 3 and d r. At the same time, however, k + m> 0 must be. In the preparation of the organosiloxane resin of general formula I, s> 0 and s + t must be equal to r.
  • resins are preferably prepared in which 5 mol% ⁇ k + m ⁇ 90 mol%, based on the sum of k, m, p, q, s and t, and preferably t is 0.
  • the radicals R 1 and R 2 are methyl radicals.
  • the units (Si0 4/2 ), ( ⁇ 3 ⁇ 0 3/2 ), (R ⁇ SiC ⁇ ), in formula I or the units (Si0 4/2 ), (R 1 Si0 3/2 ), ( R 1 2 Si0 2/2 ) in formula II can also be repeated, for example, repeatedly, for example as blocks or as individual or as alternating units occur.
  • the units (R ⁇ SiOi / a), [O 1/2 - (SiR 2 2 -XY-) a SiR 2 2 -CH 2 -OH], [Oi / 2 H] in formula I or the units (R 1 3 SiOi / 2 ), [Oi / 2 H] in formula II can occur, for example, at several points of the polymer backbone, for example ordered or randomly distributed.
  • a preferred process for the preparation of (hydroxymethyl) polysiloxanes or of (hydroxymethyl) polysiloxane resins is characterized in that as silanol-containing
  • Organosiloxanes or organosiloxane resins of the formula II are Organosiloxanes or organosiloxane resins of the formula II
  • cc is integer values from 2 to 20,000
  • R 11 is methyl, ethyl, vinyl, allyl or phenyl
  • ⁇ preferably assumes values of 3 to 10,000, preferably 4 to 1000, particularly preferably 5 to 200.
  • R is preferably methyl, ethyl, vinyl or phenyl, preferably methyl or vinyl, more preferably methyl.
  • Formula IIa is derived from formula II when in formula II the radicals R 1 are R 11 and k, m and q are all 0 and r is 2 and p is ⁇ , where oc is the value can be defined as above.
  • a preferred process for the preparation of (hydroxymethyl) -polysiloxanes or of (hydroxymethyl) polysiloxane resins is characterized in that compounds of the formula III used are compounds of the formula IIIa, Z- [O-CH 2 -SiR 12 2 ] nY
  • Formula IIIa where R 12 is methyl, ethyl, vinyl, allyl, phenyl, methoxy, ethoxy, ⁇ -propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, can accept tert-pentoxy or n-hexoxy,
  • Y and Z can assume the same meanings as defined above.
  • R 12 is preferably methyl, ethyl, vinyl, allyl, phenyl, methoxy or ethoxy, preferably methyl, ethyl, vinyl, allyl or phenyl, more preferably methyl.
  • n, Y and Z preferably assume, preferably or particularly preferably those defined above in formula III as being preferred or particularly preferred
  • R 11 and R 12 have the meanings defined above, wherein compounds of the formula IIa are reacted with compounds of the formula IIIa.
  • ⁇ preferably assumes values of 3 to 10,000, preferably 4 to 1000, particularly preferably 5 to 200.
  • ⁇ refers to the average chain lengths (number average) of the siloxanes.
  • the molar ratio of compounds of formula II, which have been selected from the possibilities defined for formulas IIa, to compounds of formula III, which were selected from the options defined for formulas IIIa, is preferably selected so that the molar ratio of
  • compounds which have a unit of the general formula III, compounds of the following general formulas IV-VIII are used
  • R 1 in formula VIII can assume the same meanings as defined above and in formula VIII preferably, preferably or particularly preferably the meanings as defined above as being preferred, preferably or particularly preferred for R 1 ,
  • R 2 in the formulas IV-VIII may assume the same meanings as defined above and in the formulas IV-VIII preferably, preferably or particularly preferably the Meanings as above as preferred, preferred
  • R 2 in preferred embodiments assumes the meaning R 12 , with the meanings defined above for R 12 , preferably, preferred and particularly preferred meanings,
  • formula V denotes an integer value greater than or equal to 0 and preferably assumes values greater than or equal to 1, preferably values of 1-20 and particularly preferably values of 1-10,
  • in formula VIII can assume a value greater than or equal to 1 and preferably the meanings 1-20, preferably 1-10, and particularly preferably takes the values 1 or 2
  • in formula VIII can assume a value greater than or equal to 0 and preferably the meanings 0 -20, preferably 0-10 and particularly preferably takes on the values 0, 1 or 2
  • in formula VIII may have a value greater than or equal to 0 and preferably the meanings 0-20, preferably 0-10 and particularly preferably the value 0, assumes .
  • Y 1 in formula VI is a radical R 2 , a radical -O- (SiR 2 2 -CH 2 - OJ b Z 1 , a hydrogen atom or a hydrolyzable group, preferably a hydroxyl group, a Ci-C 2 o
  • Y 1 represents a hydrolyzable group including alkoxy, aryloxy, hydroxy or a hydrogen atom, or represents -O- (SiR 2 2 -CH 2 -0) b H with b greater than or equal to 2,
  • b is values greater than or equal to 1 and preferably represents values greater than or equal to 2, preferably 2-30, particularly preferably 2-10
  • Y 2 in formula VII is a radical R 2 , a radical -O- (SiR 2 2 - CH 2 -O) c Z 2 , a hydrogen atom or a
  • hydrolyzable group including hydroxy group, preferably a hydroxy group, a Ci-C 20 alkoxy group, a C 6 -C 20 ⁇ ryloxy devis or a Ci-C 40
  • Polyether group in particular for a hydroxy group, a
  • c is values greater than or equal to 1 and preferably represents values greater than or equal to 2, preferably 2-30, particularly preferably 2-10,
  • Z 1 represents a hydrogen atom, one represents a silicon atom
  • Z 2 represents a hydrogen atom, one represents a silicon atom
  • hydrolyzable group is - for one optionally with Q 1 substituted or interrupted by one or more groups Q 2 alkyl, aryl or acyl group, preferably a hydrogen atom,
  • Acyl group preferably a hydrogen atom, can have the same meanings as Z 1 ,
  • i may be 2, 3, 4, 5, 6, 7, 8, 9, 10 or greater.
  • j, v, w can be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or greater.
  • ⁇ , ⁇ , ⁇ , ⁇ , ⁇ can assume the values 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or greater.
  • Z takes 4 meanings selected from groups representable by , where q is increased by 1 and w is decreased by 1.
  • the units [SiR 2 -CH 2 -O-] y and [SiR 2 -O] j in formula V can also, for example, be repeated several times, for example as blocks or as individual units or as alternating units.
  • (SiR 2 2 -XY-), (SiR 2 2 -CH 2 -O) in formula VIII can also The units (R 1 SiO 2), [O 1/2 - (SiR 2 2 -XY-) a (SiR 2 2 -CH 2 -O) iZ, occur, for example, as blocks or as individual units or as alternating units 3 ],
  • [Oi 2 Z 4] in the formula VIII can, for example, at several points of the polymer backbone, for example, orderly or randomly distributed, occur ,
  • R 12 can have the same meanings as defined above and where R 12 in formula IIIb is preferably
  • R 12 particularly preferably assumes the meanings as defined above for R 12 as being preferred, preferred or particularly preferred, and where ⁇ can assume integer values greater than or equal to 1 and preferably values of 1 to 10, preferably 1 or 2, particularly preferably 1, accepts.
  • d are integer values greater than or equal to 1, e integer values greater than or equal to 0, e 'integer values greater than or equal to 0 and f integer values of 0 or greater than or equal to 2, and where R is the meanings hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, sec-pentyl (1-methylbutyl or 1-ethylpropyl), iso-pentyl (2-methylbutyl or 3 Methylbutyl), neo-pentyl, tert-pentyl, n -hexyl, n-octyl, benzyl, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, cyclopentyl or cyclohexyl, and wherein R when f is not 0
  • integer values greater than or equal to 0 and the sum of g + h can take integer values greater than or equal to 3,
  • repeating units [-O-CH 2 -SiMe 2 ] d and [-O-SiMe 2 ] e or [SiMe 2 -O-] e 'and [SiMe 2 -CH 2 -O-] f in structure 3 can in each case be repeated repeats for example as blocks or as individual or as alternating units,
  • the repeating units [SiMe 2 -CH 2 -0-] g and [SiMe 2 -0-] h in structure 4 can be repeated several times, for example as blocks or as individual units or as alternating units,
  • Structure 3 can be prepared from the compounds of structure 1, 2 or 4 by solvolysis with water or alcohols, if appropriate in the presence of at least one catalyst.
  • the choice of the radical R in the selected solvolysis reagent ROH thereby determines the identity of the radical R in the product of the structure 3.
  • the sum of the amount of [SiMe 2 -O] group in the compounds of the structure 4 to be produced becomes zero and, accordingly, in the process in this case at least zero [Me 2 SiO] equivalents are added.
  • the pure compound 1 (> 98%, GC) can be stored at room temperature without addition of catalyst for more than 6 months without noticeable change.
  • d preferably assumes values of from 2 to 100, preferably from 2 to 30, in particular from 2 to 10.
  • e preferably assumes values of 0 to 200, preferably 0 to 10, particularly preferably 0.
  • e preferably assumes values of 0 to 200, preferably 0 to 10, particularly preferably 0.
  • f preferably has the values 0 or 2 to 100, preferably 0 or 2 to 30, particularly preferably 0.
  • R is preferably hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, benzyl, phenyl, 2 Methylphenyl, 3-methylphenyl, 4-methylphenyl, cyclopentyl or cyclohexyl
  • Hydrogen methyl, ethyl, ⁇ -propyl, n-butyl, n-pentyl, n-hexyl or ji-octyl, particularly preferably hydrogen, methyl or ethyl.
  • h preferably assumes values of from 0 to 10, preferably 0 to 5, particularly preferably 0.
  • the sum g + h preferably takes values from 3 to 20,
  • the invention further provides a method for
  • the compounds of the formula VIII are obtainable by mixing mixtures containing compounds of the general formula II and / or the general formula I preferably with a Excess of compounds of formula IV, V, VI, VII or a second compound of formula VIII and the remaining process parameters selected as described in the preparation process for compounds of formula I.
  • Excess means that the amount of substance used in total in the
  • [OCH 2 SiR 2 2 ] assumes a value greater than the molar amount of structural units [Oi / 2 H] present in total in the compounds of the formula I and II used.
  • the structural units [Oi / 2 H] present in formula I or II react to form structural units of the formula [O 1/2 - (SiR 2 2 -XY-) a (SiR 2 2 -CH 2 - 0) ⁇ Z 3] or the formula [O1 / 2 - (SiR 2 2 -XY-) a SiR 2 2 -CH 2 -O-Z 3], so that w in the animal resulted end product of formula VIII in the Usually takes the value 0; however, for example, under mild conditions, such as without added catalyst or, for example, with a mildly reactive catalyst or, for example, at mild temperatures, such as below 120 ° C, the preparation of compounds of formula VIII may be carried out such that w in the resulting product of formula VIII assume
  • the structural units [Oi / 2H] present in formula I or II can first be used to form structural units of the formula [O1 / 2 - (SiR 2 2 -XY-) a (SiR 2 2 -CH 2 -0) iZ 3 ], so that first compounds of the formula VIII are formed, where w first assumes a value greater than 0.
  • Stoichiometric means that the amount of substance in total of the structural units [OCH 2 SiR 2 ] present in the compounds of the formula IV, V, VI, VII or a second compound of the formula VIII used has a value equal to the amount of substance in total in the compounds used.
  • Compounds of the formula VIII can be converted into other compounds of the formula VIII.
  • various compounds of the formula VIII can be equilibrated with one another by exchanging the groups SiR 2 2 -CH 2 -0, or i or v in formula VIII can be increased by further reaction with compounds of the formula IV, V, VI or VII or lowered by reaction with compounds of formula I or formula II. If an excess of compounds of the formula VIII is used in the reaction of a compound of the formula VIII with a compound of the formula I or II, then i or v in the compound of the formula VIII originally used can be lowered, while the compound of the formula I used or II in turn can be converted into a novel compound of formula VIII.
  • Silylated compounds of the formula I and silylated derivatives of compounds of the general formula I can be prepared,
  • silylation reagent such as a chloro, amino, alkoxy, hydroxytrialkyl, triaryl or triarylalkylsilane,
  • III is selected from a trialkyl, triaryl or a triarylalkylsilyl group
  • R 1 and R 2 can assume the same meanings as above
  • a, k, m, p and q can assume the same values as defined above, 1 can assume an integer value greater than or equal to 2 and preferably has the meanings 2-100, preferably 2 to 30, particularly preferably 2-10,
  • x can take a value greater than or equal to 0 and
  • y can assume a value greater than or equal to 0 and
  • z can assume a value greater than or equal to 0 and
  • preferably has the meanings 0-10, preferably 0, 1 or 2, particularly preferably 0,
  • Z 5 represents a silyl group bonded via a silicon atom, a siloxane group bonded via a silicon atom or a hydrogen atom, and
  • Z 6 can assume the same meanings as Z 5 ,
  • the groups Z 5 or Z 6 must be at least partially selected from silyl groups.
  • Z 5 is preferably a silyl group or hydrogen bonded via a silicon atom, more preferably
  • Z 6 preferably represents a silyl group bonded via a silicon atom or a siloxanyl group bonded via a silicon atom, preferably a silyl group bonded via a silicon atom, more preferably
  • Trimethylsilyl triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, dimethylphenylsilyl or
  • 1 may, for example, assume the meanings 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11-30.
  • x, y and z may be 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11-20.
  • the compounds of the formula IIa are preferably used as compounds of the formula II, and the compounds of the formula IIIa, IIIb, IV, V, VI, VII or VIII, preferably of the formula IIIb, are particularly preferred compounds of the formula III
  • the compound of formula IX corresponds to a compound of formula I. This can be achieved, for example, by the silylating agent having the structure R 1 3 Si-AG, where the group AG is for a hydrolyzable leaving group.
  • the compound of formula II is before
  • the sum of the molar amount of silylating agent plus the amount of substance in groups [OCH 2 SiR 2 ] in the compound of the formula III used is stoichiometric or substoichiometric, based on the molar amount of SiOH groups in the compound of the formula II used.
  • Ci-C 20 alkoxy group a C 6 -C group 20 aryloxy group, a hydroxy group, a halogen atom, a radical bonded via nitrogen, a hydrogen atom or a group OSiR 1 3, preferably a methoxy group, an ethoxy , a hydroxy group, a chlorine atom, a hydrogen atom, a group N (H) SiR 1 3 , a group N (alkyl) SiR 1 3 , an amino, alkylamino, or dialkylamino group, an imidazole radical, or a group 0SiR 1 3 .
  • Compounds of the formula IX in which x is greater than 0 can be obtained, for example, by adding an excess
  • R 9 is hydrogen or an optionally substituted by CN or halogen Ci-Ci 0 hydrocarbon radical and
  • Ci-Cio hydrocarbon radical mean hydrogen or an optionally substituted with -CN or halogen Ci-Cio hydrocarbon radical.
  • R 10 is hydrogen.
  • Z 3 may be a silyl group, a siloxanyl group or an optionally substituted alkyl, aryl or acyl group
  • Z 4 may be a silyl group or a silyl group
  • Siloxanyl stand.
  • Groups Z 3 which are cleavable by solvolysis with protic compounds, can be partially or completely converted into hydrogen by solvolysis of compounds of formula VIII and i can be reduced to 1.
  • Z 4 is hydrogen or w is 0.
  • the groups Z 5 in compounds of the formula IX can be partially replaced by solvolysis. converted into hydrogen or w can be reduced to 1.
  • Z 6 is selected to be hydrogen or z is 0.
  • the invention further provides a process for the solvolysis of compounds or intermediates which can be obtained on addition of a silylating agent, such as solvolysis of compounds of general formula VIII or of formula IX.
  • a silylating agent such as solvolysis of compounds of general formula VIII or of formula IX.
  • the compounds of general formula VIII or IX with water, an alcohol such as methanol, ethanol, propanol or butanol, where n-, sec-, iso- or tert-isomers of the alcohols can be used, a silanol such as triethylsilanol, an OH-functional siloxane (where, for example, compounds of the formula II can be used as the OH-functional siloxane) or, if Z 3 in formula VIII represents an acyl group, also with a primary or secondary amine, for example ammonia, butylamine or diethylamine, or be reacted with a mixture containing one or more of these Solvolysereagenzien.
  • the solvolysis process preferably uses compounds of the formula VIII or IX. In the solvolysis process for compounds of the formula VIII, preference is given to
  • Parameter Z 4 is equal to hydrogen or w is chosen equal to 0 and the solvolysis of the groups Z 4 is carried out completely and i is reduced by solvolysis to 1, so that compounds of general formula I are obtained.
  • the parameters Z 6 are preferably chosen to be hydrogen or z is 0 and the solvolysis of the groups Z 4 is completed carried out and 1 is reduced by solvolysis to 1, so that compounds of general formula I are obtained.
  • the aforementioned methods can preferably be carried out at temperatures of 0 ° C to 250 ° C. However, preferred reaction temperatures of at least 10 ° C to 150 ° C.
  • the processes can be carried out uncatalyzed.
  • the processes can be improved by adding catalysts. These catalysts are acidic or basic compounds or
  • the catalyst used is preferably an inorganic or organic Lewis acid or Lewis base, or inorganic or organic Br ⁇ nsted acid or Br ⁇ nstedt base, an organometallic compound or a halide salt.
  • Preferred acids include carboxylic acids, partially esterified carboxylic acids, in particular monocarboxylic acids, preferably formic acid or acetic acid, unesterified or partially esterified mono-, oligo- or polyphosphoric acids, unhydrolysed or partially hydrolyzed phosphoroduric chloride, sulfonic acids, alkyl hydrogen sulfates or acidic ion exchangers.
  • Preferred bases are preferably alkylammonium hydroxides, ammonium alkoxides, alkylammonium fluorides or amine bases,
  • Guanidine bases or amidine bases are used. preferred
  • Metal compounds are tin compounds, zinc compounds, aluminum compounds, bismuth compounds or titanium compounds.
  • Preferred organometallic compounds are organo-tin compounds, organo-zinc compounds, organoaluminum compounds, organobismuth compounds or organotitanium compounds.
  • Preferred salts are tetraalkylammonium fluorides.
  • the catalysts used are deactivated after the functionalization reaction of the silanol groups, preferably by addition of so-called anti-catalysts or catalyst poisons, removed by distillation, decanting, centrifuging or filtration, adsorbed to a support material, precipitated, complexed or extracted before they can lead to a cleavage of the Si-O-Si groups.
  • catalyst poisons are, for example, acids in the case of the use of bases and, for example, acids in the case of the use of acids, which in the end leads to a simple neutralization reaction.
  • the corresponding reaction product between catalyst and catalyst poison can either be removed from the product or remain in the product.
  • catalysts that can be removed by distillation are carboxylic acids such as formic acid or acetic acid, or amine bases, amidine bases or guanidine bases such as triethylamine, tributylamine, ethyldiisopropylamine, ethylenediamine, tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undec -7-ene, 1, 5-diazabicyclo [4.3.0] ⁇ -5-ene or 1, 4-diazabicyclo [2.2.2] octane.
  • carboxylic acids such as formic acid or acetic acid
  • amine bases amidine bases or guanidine bases
  • amidine bases or guanidine bases such as triethylamine, tributylamine, ethyldiisopropylamine, ethylenediamine, tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undec -7-ene, 1, 5-d
  • catalysts that can be removed by decantation, filtration or by centrifuging are heterogeneous catalysts such as polymer-supported acids or bases, acidic or basic ion exchangers, or acidic or basic alumina.
  • heterogeneous catalysts such as polymer-supported acids or bases, acidic or basic ion exchangers, or acidic or basic alumina.
  • catalysts that can be adsorbed, complexed or precipitated are tin compounds, zinc compounds or titanium compounds. To be favoured
  • the distillative removable Catalysts are characterized in that, measured at the catalyst as a pure substance, at temperatures up to 300 ° C, preferably at most 250 ° C, preferably at most 210 ° C, more preferably at most 180 ° C, a vapor pressure of at least 1 hPa, preferably at least 10 hPa, preferably at least 100 hPa, more preferably
  • the amount of the compound used with units of the general formula III depends on the amount r of the silanol groups to be functionalized in the organosiloxane of the general formula II. However, if a complete functionalization of the Achieve OH groups, so the compound with units of the general formula III in at least equimolar amounts, based on n, admit.
  • organopolysiloxanes of the formula II used in the process according to the invention may comprise water which may be mixed with the compounds of the formula III or with the intermediates which may be present during the performance of the process.
  • passing compounds of formula VIII can react in hydrolysis reactions. Result is a corresponding excess consumption of compound of formula III. This can be taken into account by using correspondingly larger amounts of compound of the general formula III, preferably two moles of units of the formula III, based on n, being additionally added per mole of water. Methods for determining water such as Karl Fischer titration or headspace GC are well known.
  • hydrolysis products for example compounds of structure 3 or 1, 3-bis (hydroxymethyl) -
  • 1, 1, 3, 3-tetramethyldisiloxane or (hydroxymethyl) dimethylsilanol occur.
  • the compounds of structure 3 are assigned to the compounds of the formula III and can thus - in the absence of the described water-related increased consumption - react further in the process according to the invention.
  • the 1,3-bis (hydroxymethyl) -1, 1, 3, 3-tetramethyldisiloxane does not correspond to a compound of the formula III, since n is equal to 1 on both sides of the siloxane oxygen atom and neither of the two silicon atoms carries a hydrolyzable group.
  • hydrolysis products such as, for example, 1,3-bis (hydroxymethyl) -1,3,3,3-tetramethyldisiloxane
  • the water can be removed from the organopolysiloxane of formula II by suitable methods, for example by distillation, application of vacuum, heating, reaction with water-scavenging reagents, adsorption onto water-absorbing agents, such as molecular sieves or alumina , Drying by salts such as magnesium sulfate, sodium sulfate, calcium chloride or potassium carbonate, or by a combination of drying methods, such as by Combination of the mentioned methods, for example combination of heating and application of vacuum, as is possible for example on a thin-film or short-path evaporator.
  • the removal of the water before carrying out the process according to the invention is preferred.
  • the drying is preferably carried out until a residual water content of less than 10000 ppm, preferably less than 1000 ppm, more preferably less than 200 ppm is achieved.
  • the methods can be used both with the inclusion of
  • Solvents are carried out, or even without the use of solvents in suitable reactors. If appropriate, work is carried out under reduced pressure or under elevated pressure or under atmospheric pressure (0.1 MPa absolute). The processes can be carried out continuously or discontinuously.
  • the solvents used may be cyclic or acyclic hydrocarbons, ethers, esters, alcohols, amides, urea derivatives or halogenated organic compounds or solvent mixtures.
  • solvents inert, especially aprotic, solvents such as aliphatic hydrocarbons, e.g. Heptane or decane and aromatic hydrocarbons, e.g. Toluene or xylene preferred.
  • ethers such as tetrahydrofuran, diethyl ether or methyl tert-butyl ether.
  • the amount of solvent should be sufficient to ensure sufficient homogenization of the reaction mixture.
  • Solvent or solvent mixtures having a boiling point or boiling range of up to 120 ° C at 0.1 MPa absolute are preferred.
  • alcohols are used as solvents, they can convert various compounds of the formula III into one another.
  • methanol or ethanol may react with, for example, the compounds of structures 1, 2 or 4 to compounds of structure 3.
  • the obtained by the action of alcohols compounds of formula III can also be used in the process according to the invention.
  • (Hydroxymethyl) polysiloxanes or (hydroxymethyl) polysiloxane resins can be used for reaction with isocyanates, for the preparation of urethanes, polyurethanes or polyurethane copolymers, for reaction with carboxylic acids or with carboxylic acid derivatives, or for the preparation of esters, polyesters or polyester copolymers. All the above symbols of the above formulas have their meanings, unless expressly stated otherwise, each independently.
  • Example 1 The reaction is carried out as in Example 1, with the difference that 0.36 g of tetramethylguanidine (catalyst) (360 ppm based on Me-siloxane) are added. The reaction proceeds correspondingly slower and reaches only after 6 hours the complete conversion of the SiOH groups. The cleaning is carried out as in Example 1.
  • Example 4 The reaction is carried out as in Example 1, with the difference that 0.25 g of tetramethylguanidine (catalyst) (250 ppm based on Me-siloxane) are added. The reaction proceeds ent ⁇ speaking slowly and reached only after 12 hours to complete conversion of the SiOH groups. The cleaning is carried out as in Example 1.
  • Example 4
  • siloxane (a, ⁇ -bis-hydroxy terminated polydimethylsiloxane having a Mn of 900 g / mol, determined by "" "H-NMR Spektros- Copy; corresponding to 1.111 mol of siloxane with 2.222 mol of SiOH groups) were dissolved at 20 ° C. with 196 g (1.111 mol) of 2,2,5,5-tetramethyl-2,5-diol-1,4-dioxacyclohexane (compound 1) and 0.5 g of tetramethylguanidine (catalyst) (500 ppm based on siloxane).
  • siloxane a, ⁇ -bis-hydroxy terminated polydimethylsiloxane having a Mn of 900 g / mol, determined by "" "H-NMR Spektros- Copy; corresponding to 1.111 mol of siloxane with 2.222 mol of SiOH groups
  • Me-siloxane (a, w-bishydroxy-terminated polydimethylsiloxane having a Mn of 2930 g / mol, determined by 1 H NMR
  • Example shows that both 2, 2, 5, 5-tetramethyl-2, 5-disila-l, 4-dioxacyclohexan and its oligomers are suitable for the derivatization of SiOH groups.
  • Example 2 The reaction is carried out as in Example 1, with the difference that 0.1 g (100 ppm) Natriunnethanolat (catalyst) were used in place of tetramethylguanidine.
  • the reaction mixture was stirred at 20-30 ° C for 90 minutes, then the catalyst was neutralized by the addition of stoichiometric amounts of acetic acid (formation of sodium acetate).
  • the mixture was stirred for a further 60 minutes at 20-30 ° C, the neutralization product methanol was removed in vacuo and precipitated sodium acetate was filtered off. Pure ⁇ , ⁇ -bis (hydroxymethyl) polydimethylsiloxane was obtained.
  • silicone oil et, ⁇ -bis-hydroxy terminated siloxane with a vinyl Polymethylvinyl-: Methyl ratio of 1: 4 and a Mn of 2800 g / mol, determined by "" "H-NMR spectroscopy;
  • siloxane oc, ⁇ -bis-hydroxy terminated polydimethylsiloxane determined by ⁇ having an Mn of 1336 g / mol, "H-NMR spectroscopy; corresponding to 2.545 mmol siloxane with SiOH groups 5.09 mmol
  • compound 1 2,2,5,5-tetramethyl-2,5-disila-1,4-dioxacyclohexane (compound 1) and 170 mg of basic aluminum oxide (Brockmann activity I)
  • a product prepared according to Example 8 was 4.17 g
  • Siloxane (, ⁇ -bishydroxy-terminated polydimethylsiloxane with a Mn of 1336 g / mol, determined by 1 H-NMR spectroscopy, corresponding to 3.12 mmol siloxane with 6.24 mmol SiOH groups).
  • the mixture was stirred at 120 ° C for 2 hours.
  • 1 H-NMR showed that after 2 hours all SiOH groups with Si-O- [(SiMe 2 -CH 2 -0) iH] units to Si-0-SiMe 2 -CH 2 OH units
  • a product prepared according to Example 8 was 1.00 g
  • Me-siloxane ( ⁇ -bishydroxy-terminated polydimethylsiloxane) having a Mn of 3557 g / mol, determined by 1 H-NMR spectroscopy; corresponding to 56.6 mmol of polydimethylsiloxane with 113 mmol of SiOH groups) were mixed at 50 ° C.
  • Compound 1 (proportion of the mixture: 24%, GC) the compounds of the structures 4a-4u detectable, mainly the compounds 4a-e.
  • the compounds of structures 4a-4s were detectable by GC and GC / MS in addition to compound 1 (proportion of the mixture: 7%, GC) (GC: 4a 38%, 4b 11%, 4c 1%, 4d 2.5%, 4e 14%, 4k 1%, 4u 4%; the remainder consisted of other compounds of structure 4).

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Abstract

L'invention concerne un procédé de production d'(hydroxyméthyl)polysiloxanes de la formule générale (I), (S iO4/2 ) k (R1SiO3/2 ) m ( R1SiO2/2 ) p ( R1 3SiO1/2) q [ O1/2- ( S iR2 2-X-Y- ) aSiR2 2-CH2-OH ] s [ O1/2H ] t, selon lequel on fait réagir des organosiloxanes contenant du silanol de la formule générale (II), (SiO4/2 ) k ( R1SiO3/2 ) m ( R1 2SiO2/2 ) p ( R1 3SiO1/2) q [ O1/2H] r, avec des composés cycliques ou acycliques qui présentent au moins une unité de la formule générale (III) Z-[O-CH2-SiR2 2]n-Y, R1 signifiant un atome d'hydrogène ou un reste hydrocarbure en C1-C20 ou un reste oxyhydrocarbure en C1-C20 ou un reste polyéther en C4-C40 éventuellement substitué par Q1, éventuellement interrompu par un ou plusieurs groupes Q2 contenant des hétéroatomes, cyclique ou acyclique, linéaire ou ramifié, aromatique ou aliphatique ou oléfinique, saturé ou insaturé, R2 signifiant un reste hydrocarbure en C1-C20 ou un reste oxyhydrocarbure en C1-C20 ou un reste polyéther en C4-C40 ou un reste siloxanyle en Si1-Si2O, éventuellement substitué par Q1, éventuellement interrompu par un ou plusieurs groupes Q2 contenant des hétéroatomes ou contenant un ou plusieurs groupes Q2 contenant des hétéroatomes, cyclique ou acyclique, linéaire ou ramifié, aromatique ou aliphatique ou oléfinique, saturé ou insaturé, Q1 signifiant un reste monovalent contenant des hétéroatomes, Q2 signifiant un reste bivalent contenant des hétéroatomes ou un reste trivalent contenant des hétéroatomes, Z représentant de l'hydrogène, un groupe X-SiR2 2-, ou avec Y une paire d'électrons de liaison, X un groupe R2, un groupe siloxane ou une paire d'électrons de liaison par rapport Y ou peut être lié à Y ou X avec Y signifie un atome d'oxygène ou signifie un atome d'oxygène lié à Y, Y pouvant prendre des significations choisies parmi les significations de R2 ou Q1 ou Q2 ou représentant un reste siloxane ou un groupe hydrolysable incluant le groupe hydroxy ou avec Z une paire d'électrons de liaison et peut être lié à Z via X et peut être interrompu par un ou plusieurs groupes silane éventuellement substitués ou signifie avec S un atome d'oxygène, pour autant que Y, quand n = 1, signifie un groupe hydrolysable ou un reste siloxane qui comprend au moins un groupe hydrolysable, ou avec X un atome d'oxygène ou soit relié à X ou représente avec Z une liaison, s signifie des valeurs d'au moins 1, r des valeurs d'au moins 1, t des valeurs d'au moins 0, n des valeurs d'au moins 1, la somme s + t la valeur de r, k, m, p, q des valeurs supérieurs ou égales à zéro, pour autant que la somme k + m + p + q signifie une somme d'au moins 2, a prend la valeur 0 ou 1.
EP10763727.4A 2009-10-30 2010-10-14 Procédé de production d'(hydroxyméthyl)polysiloxanes Not-in-force EP2493962B1 (fr)

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PCT/EP2010/065451 WO2011051108A1 (fr) 2009-10-30 2010-10-14 Procédé de production d'(hydroxyméthyl)polysiloxanes

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DE102010003110A1 (de) * 2010-03-22 2011-09-22 Wacker Chemie Ag Herstellung von Silaoxacyclen
DE102011080888A1 (de) 2011-08-12 2013-02-14 Technische Universität München Verfahren zur Herstellung von poly(hydroxymethyl)-funktionellen Siloxanen und Kieselgelen
DE102011080900A1 (de) 2011-08-12 2013-02-14 Wacker Chemie Ag Verfahren zur Herstellung von (Hydroxymethyl)polysiloxanen
DE102012013710A1 (de) 2012-07-11 2014-01-16 Technische Universität München Vernetzbare Siloxane durch säurekatalysierte Polymerisation von Oxasilacyclen
DE102012013711A1 (de) 2012-07-11 2014-01-16 Technische Universität München Oxasilacyclen und Verfahren zu deren Herstellung
WO2018110613A1 (fr) * 2016-12-13 2018-06-21 三菱ケミカル株式会社 Polyorganosiloxane, composition de polyorganosiloxane, produit durci, solution électrolytique contenant un polyorganosiloxane pour condensateur électrolytique, et condensateur électrolytique utilisant celle-ci
CN111690138B (zh) * 2020-07-16 2022-04-19 江西蓝星星火有机硅有限公司 低粘度乙烯基羟基硅油及其制备方法

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DE102009046254A1 (de) 2011-05-19
KR20120093244A (ko) 2012-08-22
JP5628330B2 (ja) 2014-11-19
US8822621B2 (en) 2014-09-02
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US20120220793A1 (en) 2012-08-30
KR101507483B1 (ko) 2015-04-07

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